Multi-layer printed circuit board and method of manufacturing multi-layer printed circuit board

ABSTRACT

Through holes  36  are formed to penetrate a core substrate  30  and lower interlayer resin insulating layers  50 , and via holes  66  are formed right on the through holes  36 , respectively. Due to this, the through holes  36  and the via holes  66  are arranged linearly, thereby making it possible to shorten wiring length and to accelerate signal transmission speed. Also, since the through holes  36  and the via holes  66  to be connected to solder bumps  76  (conductive connection pins  78 ), respectively, are directly connected to one another, excellent reliability in connection is ensured.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of and claims the benefit of priorityunder 35 U.S.C. §120 from U.S. Ser. No. 11/333,228, filed Jan. 18, 2006which is a divisional of the U.S. Ser. No. 11/106,642, filed Apr. 15,2005, now U.S. Pat. No. 7,178,234, issued Feb. 20, 2007, and is adivisional of U.S. Ser. No. 09/830,963, filed Jul. 6, 2001, now U.S.Pat. No. 6,930,258, issued Aug. 16, 2005, which is a national state ofPCT/JP00/07037, filed Oct. 10, 2000, and claims priority under 35 U.S.C.§119 to Japanese Patent Application No. 11-303305, filed Oct. 26, 1999;11-303306, filed Oct. 26, 1999; 11-303307, filed Oct. 26, 1999; and2000-029988, filed Feb. 8, 2000.

TECHNICAL FIELD

The present invention relates to a multi-layer printed circuit boardhaving buildup layers formed on the both sides of a core substrate, thebuildup layers each having interlayer resin insulating layers andconductor layers alternately provided, the conductor layers connected toone another by via holes. More particularly, the present inventionrelates to a multi-layer printed circuit board and a method ofmanufacturing a multi-layer printed circuit board which can be employedas a package substrate on which IC chips can be mounted.

BACKGROUND ART

Hitherto, a buildup multi-layer printed circuit board has beenmanufactured by a method disclosed by, for example, Japanese PatentLaid-Open No. 9-130050.

A rough layer is formed on the surface of the conductor circuit of aprinted circuit board by electroless plating or etching. Then, aninterlayer insulating resin is applied, exposed and developed by a rollcoater or printing, via hole opening portions are formed for makinglayers continuous, and an interlayer resin insulating layer is formedthrough UV hardening, actual hardening and the like. Further, a catalystsuch as palladium is applied on to the interlayer resin insulating layeron the rough surface which has been subjected to a roughing process withan acid or an oxidizer. A thin electroless plated film is formed, apattern is formed on the plated film by a dry film and the thickness ofthe pattern is increased by electroplating. Thereafter, the dry film isseparated and removed by an alkali and etched to thereby form aconductor circuit. By repeating the above processes, a buildupmulti-layer printed circuit board is obtained.

At present, as the frequency of IC chips becomes higher, demand foraccelerating the transmission speed of a multi-layer printed circuitboard rises. To deal with such demand, the applicant of the presentinvention proposed Japanese Patent Laid-Open No. 10-334499. With thisconstitution, linear wirings are provided by arranging via holes 346 ofa lower interlayer resin insulating layer 350 and via holes 366 of anupper interlayer resin insulating layer 360 right above through holes336, thereby shortening wiring lengths and accelerating signaltransmission speed.

It was discovered, however, that with the above constitution, the viaholes 346 of the lower interlayer resin insulating layer 350 and the viaholes 366 of the upper interlayer resin insulating layer 360 areseparated from one another under heat cycle conditions. The inventor ofthe present invention investigated the cause of separation anddiscovered that the via holes 366 in the upper layer are influenced bythe shapes of the surfaces of the via holes 346 of the lower layer andthe connection characteristic of the via holes 366 deteriorates.Further, it is estimated that since the interlayer resin insulatinglayers 350 and 360 are not reinforced by core materials such as glasscloth, these layers tend to be separated in a heat cycle rather than acore substrate provided with a core material.

The present invention has been made to overcome the foregoing problems,and it is, therefore, an object of the present invention to provide amulti-layer printed circuit board and a method of manufacturing amulti-layer printed circuit board capable of shortening internal wiringlengths and having excellent connection reliability.

It is a still further object of the present invention to provide amanufacturing method capable of manufacturing a multi-layer printedcircuit bard at low cost.

Meanwhile, a resin is filled in through holes so as to enhancereliability for a buildup multi-layer printed circuit board. Whenfilling the resin, blackening-reduction processes are conducted to thesurfaces of the through holes and rough layers are provided thereon soas to increase adhesiveness. In addition, as the density of themulti-layer printed circuit board increases, through holes are madesmaller in size. Following this, resin filler having low viscosity isemployed to be filled in the through holes.

As prior art for forming a rough layer on a through hole and filling thethrough hole with resin filler, it is described in Japanese PatentLaid-Open No. 9-181415 that a copper oxide layer is formed in a throughhole, the through hole is filled with resin filler and then aninterlayer insulating layer is formed. It is also described in JapanesePatent Laid-Open No. 9-260849 that after forming a rough layer in athrough hole by etching, the through hole is filled with resin fillerand then an interlayer insulating layer is formed.

If using resin filler having low viscosity, however, the resin filler isdented in the through hole, causing disconnection and the like duringthe formation of wirings on an upper layer. The inventor of the presentinvention investigated the cause of disconnection and discovered thatthis is because the resin out of filler and the resin which constituteresin filler flow along the rough layer (very small anchor) formed onthe land of the through hole. As a result, the filler within the throughhole is dented, making it impossible to flatten and smooth a coresubstrate. Due to this, it was discovered that if manufacturing amulti-layer printed circuit board by forming an interlayer resininsulating layer and wirings on a core substrate, the resultantmulti-layer resin insulating layer is susceptible to disconnection and aprobability of generating defects increases.

The present invention has been made to solve the foregoing problems andit is, therefore, a still further object of the present invention toprovide a method of manufacturing a multi-layer printed circuit boardhaving enhanced wiring reliability.

In the meantime, a substrate on which a resin film for the interlayerresin insulating layer of a resin substrate serving as a core materialis bonded, is employed as a core substrate. Through holes forpenetrating the substrate are filled with resin filler. Further, aninterlayer resin insulating layer is formed and via holes are formedtherein. The above-stated resin filler, however, had some defects.

First, if a reliability test such as a heat cycle is conducted to aprinted circuit board filled with filler, conductors sometimes crack inthe vicinity of the boundary between the resin substrate and the resinfilm. Second, after filling the filler, a resin film serving as aninterlayer resin insulating layer cracks in a polishing step conductedto flatten the board. Third, if a plated cover is formed right on thethrough hole, the reaction of the plated film may stop. Thus, even ifvia holes are formed right above the through holes, electricalconnection cannot be established.

As a result of these three defects, a printed circuit board withdeteriorated reliability and reduced electrical connectioncharacteristics is provided.

It is a still further object of the present invention to provide aprinted circuit board and a method of manufacturing a printed circuitboard capable of solving these defects.

DISCLOSURE OF THE INVENTION

In order to solve the above problems, a multi-layer printed circuitboard according to the claim 1 is characterized by having buildup layersformed on both sides of a core substrate, the buildup layers each havinginterlayer resin insulating layers and conductive layers alternatelyprovided, the conductor layers connected to one another by via holes,wherein

through holes are formed to penetrate said core substrate and theinterlayer resin insulating layers formed on the both sides of the coresubstrate; and

the via holes are formed right on said through holes, the via holesconnected to external connection terminals.

In claim 2, A multi-layer printed circuit board according to claim 1,wherein

resin filler is filled in said through holes and the conductor layersare formed to cover exposed surfaces of the resin filler from thethrough holes; and

the via holes right on said through holes are formed on said conductorlayers of said through holes.

According to claim 3, a method of manufacturing a multi-layer printedcircuit board comprising at least the following steps (a) to (d):

(a) forming lower interlayer resin insulating layers on both sides of acore substrate, respectively;

(b) forming through holes penetrating said core substrate and said lowerinterlayer resin insulating layers;

(c) forming upper interlayer resin insulating layers on said lowerinterlayer resin insulating layers, respectively; and

(d) forming via holes in said upper interlayer resin insulating layers,the via holes connected to external connection terminals and formedright on part of said through holes.

According to claim 4, a method of manufacturing a multi-layer printedcircuit board comprising at least the following steps (a) to (g):

(a) forming lower interlayer resin insulating layers on both sides of acore substrate, respectively;

(b) forming through holes penetrating said core substrate and said lowerinterlayer resin insulating layers;

(c) filling resin filler in said through holes;

(d) polishing and flattening the resin filler pouring from said throughholes;

(e) forming conductor layers covering exposed surfaces of said resinfiler from said through holes;

(f) forming upper interlayer resin insulating layers on said lowerinterlayer resin insulating layers, respectively; and

(g) forming via holes in said upper interlayer resin insulating layersand forming the via holes right on part of said through holes so as tobe connected to external connection terminals.

According to the multi-layer printed circuit board recited in claim 1and the method of manufacturing the multi-layer printed circuit boardrecited in claim 3, the through holes are formed to penetrate the coresubstrate and the interlayer resin insulating layers formed on the bothsides of the core substrate, and the via holes connected to externalconnection terminals are formed right on the through holes,respectively. Due to this, the through holes and the via holes arearranged linearly, thereby making it possible to shorten wiring lengthand accelerate signal transmission speed. Further, since the throughholes and the via holes connected to the external connection terminalsare directly connected to one another, connection reliability isexcellent.

According to the multi-layer printed circuit board recited in claim 2and the method of manufacturing the multi-layer printed circuit boardrecited in claim 4, the through holes are formed to penetrate the coresubstrate and the interlayer resin insulating layers formed on the bothsides of the core substrate, and the via holes are formed right on thethrough holes, respectively. Due to this, the through holes and the viaholes are arranged linearly, thereby making it possible to shortenwiring length and accelerate signal transmission speed. Further, sincethe through holes and the via holes connected to the external connectionterminals are directly connected to one another and the via holes areformed on the respective conductor layers covering the resin filler inthe through holes which filler has been flattened by polishing,connection reliability is excellent.

According to claim 5, a multi-layer printed circuit board havinginterlayer resin insulating layers on both sides of a core substrate,respectively, through holes provided to penetrate the core substrate andfilled with resin filler, the interlayer resin insulating layers andconductor circuits provided, wherein

said resin filler contains an epoxy resin, a curing agent and 10 to 50%of inorganic particles.

According to claim 6, a multi-layer printed circuit board havinginterlayer resin insulating layers formed on both sides of a coresubstrate, respectively, through holes provided to penetrate the coresubstrate and filled with resin filler, plated covers provided, theinterlayer resin insulating layers and conductor circuits provided,wherein

said resin filler contains an epoxy resin, a curing agent and 10 to 50%of inorganic particles.

According to claim 7, a multi-layer printed circuit board according toclaim 5 or 6, wherein

said inorganic particles contain one type or more selected from a groupconsisting of aluminum compounds, calcium compounds, potassiumcompounds, magnesium compounds and silicon compounds.

First, since the quantity of the mixed inorganic particles is setappropriately, the coefficient of thermal expansion of the resin filler,that of the resin substrate forming the core substrate and those of theresin films for the interlayer resin insulating layers are matched toone another. Due to this, even on heat cycle conditions, a stress causedby heat contraction does not occur. Thus, cracking does not occur.Further, the resin films are impregnated with soluble particles forforming rough surfaces by a roughing process. Due to this, it wasdiscovered that if the quantity of mixed inorganic particles exceeds50%, the matching cannot be ensured.

Second, it was discovered that in the polishing step conducted toflatten the filler after the filler is filled, the filler can be easilypolished. It was discovered that if the quantity of mixed inorganicparticles exceeds 50%, the filler can be flattened only by mechanicalpolishing using abrasive paper. The resin films on the surface layers ofthe core substrate are not impregnated with a reinforcing material suchas glass epoxy and inferior, in strength, to the resin substrate. Due tothis, if mechanical polishing with abrasive paper (such as belt sanderpolishing) is conducted, the resin films cannot resist the polishing. Asa result, the resin films crack. Besides, the resin films are damaged,thereby detaching soluble particles. Consequently, even if the roughsurfaces are formed, they are not what are desired. Considering this, ifa polishing process is performed, the surface layers of the coresubstrate are traced with a nonwoven fabric containing a polishingmaterial such as a buff, thereby removing and flattening the resinfiller.

Third, it was discovered that in the formation of plated covers right onthe respective through holes, if an inorganic particle content exceeds50%, the quantity of added catalyst decreases and the reaction of theplated films stops. The coordinate bond between the inorganic particlesand the catalyst does not occur. The quantity of added catalyst,therefore, decreases. Further, in the formation of the plated films, ifthe quantity of inorganic particles is excessive, a plating solutiontends not to be contacted, thereby stopping the reaction of the platedfilms.

If the quantity of mixed inorganic particles is less than 10%, theeffect of matching the coefficients of thermal expansion is notexpected. As a result, if the resin filler is filled, the resin filleris not left in the through holes and flows away from the other side.

It is more preferable that the mixture ratio of inorganic particles is20 to 40%. In that range, even if particles flocculate, the above-stateddefects can be avoided.

According to claim 8, a multi-layer printed circuit board according toclaim 5 or 6, wherein

a shape of said inorganic particles is one of a spherical shape, acircular shape, an ellipsoidal shape, a pulverized shape and a polygonalshape.

Preferably, the particles are circular, ellipsoidal or the like withoutangular surfaces. This is because cracks resulting from such particlesdo not occur. It is also preferable that the particle diameter of theinorganic particles is in a rage of 00.1 to 5 μm. If the particlediameter is less than 0.01 μm, the particles are offset one another whenthe resin filler is filled. If exceeding 5 μm, it is often difficult toadjust the mixture ratio of the inorganic particles in the resin.

In claim 9, a multi-layer printed circuit board according to claim 5 andclaim 6, wherein

rough layers are provided on the conductor layers of said through holes,respectively.

It is preferable that rough layers are provided on the conductor layersof the through holes, respectively. By doing so, it is possible toprevent the resin filler from expanding and contracting, whereby theinterlayer resin insulating layers and the plated covers formed on therespective through holes are not pushed up. The rough layers are formedby an oxidization-reduction process, a blackening process or a platingprocess as well as by an etching process.

According to claim 10, a method of manufacturing a multi-layer printedcircuit board having interlayer resin insulating layers provided on bothsides of a core substrate, for forming the interlayer resin insulatinglayers through the following steps (a) to (e):

(a) a formation step of forming through holes penetrating the both sidesof the printed circuit board;

(b) a filling step of filling resin filler containing an epoxy resin and10 to 50% of inorganic particles;

(c) a drying step and a polishing step;

(d) a hardening step; and

(e) a cover plating step.

In claim 11, a method according to claim 10, wherein

in said polishing step (c), a buffing step is conducted at least once ora plurality of times.

In claim 12, a method according to claim 10 or 11, wherein

in said step (a), a step of forming rough layers is conducted.

In order to achieve the above problems, in claim 13, a multi-layerprinted circuit board having buildup layers on both sides of a coresubstrate, respectively, said buildup layer having interlayer resininsulating layers and conductor layers alternately provided, theconductor layers connected to one another by via holes, wherein

through holes filled with resin filler are formed to penetrate said coresubstrate and lower interlayer resin insulating layers formed on theboth sides of the core substrate; and

via holes filled with said resin filler are formed in said lowerinterlayer resin insulating layers.

In case of the multi-layer printed circuit board recited in claim 13,the through holes and the via holes are filled with the same resinfiller. Due to this, the multi-layer printed circuit board can bemanufactured at low cost and the strength within the through holes andthat within the via holes can be kept uniform, thereby making itpossible to enhance the reliability of the multi-layer printed circuitboard.

The resin may be a thermosetting resin which means an epoxy resin, aphenol resin, a fluorocarbon resin, a triazine resin, a polyolefinresin, a polyphenylene ether resin and the like, a thermoplastic resinor a complex thereof. Inorganic filler, such as silica or alumina, maybe contained in the resin to adjust the coefficient of thermal expansionof the resin. A paste mainly consisting of metal filler such as aconductive resin, gold or silver may be employed. The complexes thereofmay be employed, as well.

In claim 14, a multi-layer printed circuit board according to claim 13,wherein

the conductor layers are formed to cover exposed surfaces of the resinfiller filled in the via holes of said lower interlayer resin insulatinglayers; and

via holes are formed right on the via holes through the conductivelayers, respectively.

According to claim 14, the conductor layers covering the exposedsurfaces of the filler filled in the via holes of the lower interlayerresin insulating layers are formed and the via holes are formed right onthe via holes through the conductor layers, respectively. Due to this,the lower via holes can be formed flat and the adhesiveness between thelower via holes and the via holes formed on the corresponding via holescan be enhanced to thereby enhance the reliability of the multi-layerprinted circuit board.

According to claim 15, a method of manufacturing a multi-layer printedcircuit board comprising at least the following steps (a) to (g):

(a) forming lower interlayer resin insulating layers on both sides of acore substrate, respectively;

(b) forming penetrating holes in said core substrate and said lowerinterlayer resin insulating layers, the penetrating holes becomingthrough holes;

(c) forming openings in said lower interlayer resin insulating layers,the openings becoming via holes;

(d) forming conductive films in said penetrating holes and said openingsto thereby provide the through holes and the via holes, respectively;

(e) filling resin filler in said through holes and said via holes;

(f) polishing and flattening the resin filler pouring out of saidthrough holes and said via holes; and

(g) forming conductor layers covering exposed surfaces of said resinfiller from said through holes and said via holes, respectively.

According to claim 16, a method of manufacturing a multi-layer printedcircuit board comprising at least the following steps (a) to (i):

(a) forming lower interlayer resin insulating layers on both sides of acore substrate, respectively;

(b) forming penetrating holes in said core substrate and said lowerinterlayer resin insulating layers, the penetrating holes becomingthrough holes;

(c) forming openings in said lower interlayer resin insulating layers,the openings becoming via holes;

(d) forming conductive films in said penetrating holes and said openingsto provide the through holes and the via holes;

(e) filling resin filler in said through holes and said via holes;

(f) polishing and flattening the resin filler pouring out of saidthrough holes and said via holes;

(g) forming conductor layers covering exposed surfaces of said resinfiller from said through holes and said via holes;

(h) forming upper interlayer resin insulating layers on said lowerinterlayer resin insulating layers, respectively; and

(i) forming via holes in said upper interlayer resin insulating layersand right on part of said via holes.

According to the method of manufacturing the multi-layer printed circuitboard recited in claims 15 and 16, the same resin filler is filled inthe through holes and the via holes and polished simultaneously. Due tothis, the multi-layer printed circuit board can be manufactured at lowcost and the strength within the through holes and that within the viaholes can be kept uniform, so that the reliability of the multi-layerprinted circuit board can be enhanced. Further, since the upper viaholes are formed on the conductor layers covering the filler within thevia holes which filler has been polished and thereby flattened,respectively, connection reliability is excellent.

In order to achieve the above problems, according to claim 17, a methodof manufacturing a multi-layer printed circuit board comprising at leastthe following steps (a) to (e):

(a) forming lower interlayer resin insulating layers on both sides of acore substrate, respectively;

(b) forming penetrating holes in said core substrate and said lowerinterlayer resin insulating layers, the penetrating holes becomingthrough holes;

(c) forming openings in said lower interlayer resin insulating layers,the openings becoming via holes;

(d) conducting a de-smear process to said penetrating holes by an acidor an oxidizer and conducting a roughing process to surfaces of thelower interlayer resin insulating layers; and

(e) forming conductive films on said penetrating holes and said openingsto provide the through holes and the via holes, respectively.

According to the method of manufacturing the multi-layer printed circuitboard recited in claim 17, the de-smear process for the penetratingholes by employing an oxidizer and the roughing process for the surfacesof the lower interlayer resin insulating layers are performedsimultaneously. Due to this, it is possible to reduce the number ofmanufacturing steps and to manufacture the multi-layer printed circuitboard at low cost.

In claim 18, a method according to claim 17, wherein

said core substrate is made of one of a glass epoxy resin, an FR4 resin,an FR5 resin and a BT resin;

each of said lower interlayer resin insulating layers contains at leastone of an epoxy resin, a phenol resin, a polyimide resin, apolyphenylene resin, a polyolefin resin and a fluorocarbon resin; and

said oxidizer contains one of a chromic acid and permanganate.

According to claim 18, the core substrate is made of one of a glassepoxy resin, a FR4 resin, a FR5 resin and a BT resin. Each of the lowerinterlayer resin insulating layers contains at least one of an epoxyresin, a phenol resin, a polyimide resin, a polyphenylene resin, apolyolefin resin and a fluorocarbon resin. The oxidizer contains one ofa chromic acid and permanganate. Due to this, it is possible tosimultaneously perform the de-smear process for the penetrating holesfor forming the lower interlayer resin insulating layers on the coresubstrate and the roughing process for the lower interlayer resininsulating layers.

In order to achieve the above problems, according to claim 21, a methodof manufacturing a multi-layer printed circuit board comprising at leastthe following steps (a) to (d):

(a) forming through holes in a core substrate;

(b) forming rough layers on said through holes, respectively;

(c) polishing and flattening surfaces of lands of said through holes;and

(d) filling resin filler in said through holes and forming resin layers.

According to claim 21, after forming the rough layers on the throughholes, respectively, the surfaces of the lands of the through holes arepolished and flattened. By doing so, it is possible to prevent the resinfiller from flowing out along the rough layers (anchors) formed on thelands of the through holes when filling the resin filler in the throughholes. Thus, it is possible to smoothly form the filler in the throughholes and to enhance the reliability of wirings formed above the throughholes.

In claim 22, a method according to claim 21, wherein said rough layersare copper oxide layers.

In claim 23, a method according to claim 21, wherein said rough layersare formed by etching.

In claim 24, a method according to claim 21, wherein said rough layersare needle alloy layers made of copper-nickel-phosphorous.

According to claims 22, 23 and 24, the rough layer formed on eachthrough hole is preferably formed by one of the formation of a copperoxide layer by a blackening-reduction process, the formation of a needlealloy layer consisting of copper-nickel-phosphorous and by etching. Bydoing so, it is possible to enhance the adhesiveness between theconductor layers on the inner walls of the through holes and the resinfiller.

In claim 25, a method according to claims 21, wherein

said resin filler is one selected from a group consisting of a mixtureof an epoxy resin and organic filler, a mixture of an epoxy resin andinorganic filler and a mixture of an epoxy resin and inorganic fiber.

According to claim 25, the resin filler to be employed is preferably oneselected from a group consisting of a mixture of an epoxy resin andorganic filler, a mixture of an epoxy resin and inorganic filler and amixture of an epoxy resin and inorganic filler. By doing so, it ispossible to adjust the coefficients of thermal expansion between theresin filler and the core substrate.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram showing a process for manufacturing a multi-layerprinted circuit board according to the first embodiment of the presentinvention;

FIG. 2 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first embodiment;

FIG. 3 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first embodiment;

FIG. 4 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first embodiment;

FIG. 5 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first embodiment;

FIG. 6 is a cross-sectional view of the multi-layer printed circuitboard according to the first embodiment;

FIG. 7 is a table showing the evaluation results of the first embodimentand Comparison;

FIG. 8 is a diagram showing a process for manufacturing a multi-layerprinted circuit board according to the second embodiment of the presentinvention;

FIG. 9 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the second embodiment;

FIG. 10 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the second embodiment;

FIG. 11 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the second embodiment;

FIG. 12 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the second embodiment;

FIG. 13 is a cross-sectional view of the printed circuit board accordingto the second embodiment;

FIG. 14 is a diagram showing a process for manufacturing a multi-layerprinted circuit board according to the first modification of the secondembodiment;

FIG. 15 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first modification of the secondembodiment;

FIG. 16 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first modification of the secondembodiment;

FIG. 17 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first modification of the secondembodiment;

FIG. 18 is a diagram showing a process for manufacturing the multi-layerprinted circuit board according to the first modification of the secondembodiment;

FIG. 19 is a cross-sectional view of the multi-layer printed circuitboard according to the first modification of the second embodiment;

FIG. 20 is a cross-sectional view of the multi-layer printed circuitboard according to the second modification of the second embodiment;

FIG. 21 is a table showing the estimation result of the embodiments ofthe present invention and Comparisons; and

FIG. 22 is a cross-sectional view of a conventional multi-layer printedcircuit board.

BEST MODE FOR CARRYING OUT THE INVENTION First Embodiment

The embodiments of the present invention will be described hereinafterwith reference to the accompanying drawings.

First, the constitution of a multi-layer printed circuit board accordingto the first embodiment of the present invention will be described withreference to FIG. 6 showing a longitudinal sectional view.

As shown in FIG. 6, a multi-layer printed circuit board 10 has a coresubstrate 30 having right and reverse sides on which buildup wiringlayers 80U and 80D are formed, respectively. Each of the buildup wiringlayers 80U and 80D consists of a lower interlayer resin insulating layer50 in which via holes 46 are formed, an upper interlayer resininsulating layer 60 in which upper via holes 66 are formed, and a solderresist layer 70 formed on the upper interlayer resin insulating layer60. A solder bump (external connection terminal) 76 for connecting theboard 10 to an IC chip (not shown) is formed on each of the upper viaholes 66 through the opening portion 71 of the solder resist 70. Aconductive connection pin (external connection terminal) 78 forconnecting the circuit board 10 to a daughter board (not shown) isconnected to each of the lower via holes 66.

In the first embodiment, through holes 36 connecting the buildup wiringlayers 80U and 80D to each other are formed to penetrate a coresubstrate 30 and the lower interlayer resin insulating layers 50. Resinfiller 54 is filled in the through holes 36 and plated covers 58 areprovided onto the opening portions of the holes 36. Likewise, resinfiller 54 is filled in the via holes 46 formed in the lower interlayerresin insulating layer 50 and plated covers 58 are provided onto theopening portions of the via holes 46.

In the first embodiment, the through holes 36 are formed to penetratethe core substrate 30 and the lower interlayer resin insulating layers50 and the via holes 66 are formed right on the through holes 36,respectively. Due to this, each through hole 36 and each via hole 66 arearranged linearly to thereby make it possible to shorten wiring lengthand to accelerate signal transmission speed. Further, since the throughholes 36 are directly connected to the via holes 66 connected to theexternal connection terminals (solder bumps 76, conductive connectionpins 78), excellent connection reliability is obtained. In the firstembodiment, as will be described later, the filler 54 filled in thethrough holes 36 is flattened by polishing and then the plated covers(conductive layers) 58 covering the filler 54 are arranged and the viaholes 66 are formed thereon. Due to this, the surfaces of the throughholes 36 have high flatness and reliability in the connection betweenthe through holes 36 and the corresponding via holes 66 is excellent.

Furthermore, in case of the multi-layer printed circuit board in thefirst embodiment, the through holes 36 and the lower via holes 46 arefilled with the same resin filler 54 and the resin filler 54 issimultaneously polished and flattened as will be described later. Thus,the multi-layer printed circuit board can be manufactured at low costand the strength of the interiors of the through holes and that of theinteriors of the via holes can be kept uniform, so that the reliabilityof the multi-layer printed circuit board can be enhanced. Also, as willbe described later, the filler 54 filled in the via holes 47 isflattened by polishing and then the plated covers (conductive layers) 58covering the filler 54 are arranged and the upper via holes 66 areformed thereon. Due to this, the surfaces of the lower via holes 46 havehigh flatness and reliability in the connection between the lower viaholes 46 and the upper via holes 66 is excellent.

Moreover, as will be described later, in case of the multi-layer printedcircuit board in the first embodiment, a de-smear process forpenetrating holes 35 which become the through holes 36 and a roughingprocess for the surface of the lower interlayer resin insulating layer40 are performed simultaneously using an oxidizer, so that the number ofmanufacturing steps can be reduced and the multi-layer printed circuitboard can be manufactured at low cost.

Next, description will be given to a method of manufacturing themulti-layer printed circuit board with reference to FIGS. 1 to 5.

(1) A copper-clad laminated plate 30A having copper foils 32 each havinga thickness of 18 μm and laminated on both sides of a substrate 30having a thickness of 0.8 mm and made of a glass epoxy resin, FR4, FR5or BT (Bismaleimide-Triazine) resin, is employed as a starting material(FIG. 1(A)). First, this copper-clad laminated plate is etched in apattern fashion, thereby forming inner-layer copper patterns 34 on theboth sides of the substrate (FIG. 1(B)).(2) After washing the substrate 30 on which the inner-layer copperpatterns 34 are formed, an etching solution containing a cupric complexand an organic acid is reacted under oxygen coexisting conditions suchas spraying or bubbling. The copper conductor of a conductor circuit isdissolved to form voids. Through these processes, a rough layer 38 isprovided on the surface of each inner-layer copper pattern 34 (FIG. 1(c)).

Alternatively, the rough layer may be provided by anoxidization-reduction process or by employing an electroless platedalloy. The rough layer thus formed has desirably a thickness in a rangeof 0.1 to 5 μm. In such a range, the separation between the conductorcircuit and the interlayer resin insulating layer less occurs.

The cupric complex is preferably a cupric complex of azoles. The cupriccomplex of azoles functions as an oxidizer for oxidizing metallic copperor the like. Azoles preferably involve diazole, triazole and tetrazole.Particularly, imidazole, 2-methylimidazole, 2-ethylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and thelike are preferable. The quantity of added cupric complex of azoles ispreferably 1 to 15 wt %. This is because the cupric complex of such aquantity is excellent in solubility and stability.

Further, to dissolve the copper oxide, an organic acid is mixed with thecupric complex of azoles. To be specific, the organic acid is preferablyat least one selected from a group consisting of formic acid, aceticacid, propionic acid, butyric acid, valeric acid, caproic acid, acrylicacid, crotonic acid, oxalic acid, malonic acid, succinic acid, glutaricacid, maleic acid, benzoic acid, glycolic acid, lactic acid, malic acidand sulfamic acid. An organic acid content is preferably 0.1 to 30 wt %.With this content, it is possible to maintain the solubility of theoxidized copper and to secure stabile solubility.

The generated cuprous complex is dissolved by the acid, combined withoxygen into a cupric complex which contributes again to the oxidizationof copper.

Furthermore, to assist in dissolving copper and oxidizing azoles,halogen ions, such as fluorine ions, chlorine ions and bromine ions, maybe added to the etching solution. The present invention can supplyhalogen ions by adding hydrochloric acid, sodium chloride or the like.The quantity of halogen ions is preferably 0.01 to 20 wt %. Halogen ionsof such a quantity ensures excellent adhesiveness between the generatedrough surface and the interlayer resin insulating layer.

The cupric complex of azoles and the organic acid (or halogen ionsaccording to necessity) are dissolved in water to thereby adjust theetching solution. Further, a commercially available etching solution,e.g., product name “MEC etch BOND” manufactured by Mec Co., Ltd., can beemployed to form a rough surface according to the present invention.

(3) A resin film 50α which becomes a lower interlayer resin insulatinglayer is bonded on each surface of the substrate 30 by vacuum crimplamination at a pressure of 5 kgf/cm² while raising temperature to 50 to150° C. (FIG. 1(D)).

The resin film contains refractory resin, soluble particles, a curingagent and other components. The materials will now be described.

The resin film for use in the resin insulating layer in themanufacturing method according to the present invention has a structurethat particles soluble in acid or an oxidizer (hereinafter called“soluble particles”) are dispersed in resin which is refractory withrespect to acid or an oxidizer (hereinafter called “refractory resin”).

The expressions “refractory” and “soluble” will now be described. Whenmaterials are immersed in solution composed of the same acid or the sameoxidizers for the same time, a material of a type which is dissolved ata relatively high dissolving rate is called a “soluble” material forconvenience. A material of a type which is dissolved at a relativelyslow dissolving rate is called a “refractory material” for convenience.

The soluble particles are exemplified by resin particles which aresoluble in acid or an oxidizer (hereinafter called “soluble resinparticles”), inorganic particles which are soluble in acid or anoxidizer (hereinafter called “inorganic soluble particles”) and metalparticles which are soluble in acid or an oxidizer (hereinafter called“soluble metal particles”). The foregoing soluble particles may beemployed solely or two or more particles may be employed.

The shape of each of the soluble particles is not limited. The shape maybe a spherical shape or a pulverized shape. It is preferable that theparticles have a uniform shape. The reason for this lies in that a roughsurface having uniformly rough pits and projections can be formed.

It is preferable that the mean particle size of the soluble particles is0.1 μm to 10 μm. When the particles have the diameters satisfying theforegoing range, particles having two or more particle sizes may beemployed. That is, soluble particles having a mean particle size of 0.1μm to 0.5 μm and soluble particles having a mean particle size of 1 μmto 3 μmm may be mixed. Thus, a more complicated rough surface can beformed. Moreover, the adhesiveness with the conductor circuit can beimproved. In the present invention, the particle size of the solubleparticles is the length of a longest portion of each of the solubleparticles.

The soluble resin particles may be particles constituted bythermosetting resin or thermoplastic resin. When the particles areimmersed in solution composed of acid or an oxidizer, the particles mustexhibit dissolving rate higher than that of the foregoing refractoryresin.

Specifically, the soluble resin particles are exemplified by particlesconstituted by epoxy resin, phenol resin, polyimide resin, polyphenyleneresin, polyolefin resin or fluorine resin. The foregoing material may beemployed solely or two or more materials may be mixed.

The soluble resin particles may be resin particles constituted byrubber. Rubber above is exemplified by polybutadiene rubber, a varietyof denatured polybutadiene rubber, such as denatured epoxy rubber,denatured urethane rubber or denatured (metha) acrylonitrile rubber, and(metha) acrylonitrile butadiene rubber containing a carboxylic group.When the foregoing rubber material is employed, the soluble resinparticles can easily be dissolved in acid or an oxidizer. That is, whenthe soluble resin particles are dissolved with acid, dissolution ispermitted with acid except for strong acid. When the soluble resinparticles are dissolved, dissolution is permitted with permanganatewhich has a relatively weak oxidizing power. When chromic acid isemployed, dissolution is permitted even at a low concentration.Therefore, retention of the acid or the oxidizer on the surface of theresin can be prevented. When a catalyst, such as palladium chloride, issupplied after the rough surface has been formed as described later,inhibition of supply of the catalyst and oxidation of the catalyst canbe prevented.

The inorganic soluble particles are exemplified by particles made of atleast a material selected from a group consisting of an aluminumcompound, a calcium compound, a potassium compound, a magnesium compoundand a silicon compound.

The aluminum compound is exemplified by alumina and aluminum hydroxide.The calcium compound is exemplified by calcium carbonate and calciumhydroxide. The potassium compound is exemplified by potassium carbonate.The magnesium compound is exemplified by magnesia, dolomite and basicmagnesium carbonate. The silicon compound is exemplified by silica andzeolite. The foregoing material may be employed solely or two or morematerials may be mixed.

The soluble metal particles are exemplified by particles constituted byat least one material selected from a group consisting of copper,nickel, iron, zinc, lead, gold, silver, aluminum, magnesium, potassiumand silicon. The soluble metal particles may have surfaces coated withresin or the like in order to maintain an insulating characteristic.

When two or more types of the soluble particles are mixed, it ispreferable that the combination of the two types of soluble particles iscombination of resin particles and inorganic particles. Since each ofthe particles has low conductivity, an insulating characteristic withthe resin film can be maintained. Moreover, the thermal expansion caneasily be adjusted with the refractory resin. Thus, occurrence of acrack of the interlayer resin insulating layer constituted by the resinfilm can be prevented. Thus, separation between the interlayer resininsulating layer and the conductor circuit can be prevented.

The refractory resin is not limited when the resin is able to maintainthe shape of the rough surface when the rough surface is formed on theinterlayer resin insulating layer by using acid or oxidizer. Therefractory resin is exemplified by thermosetting resin, thermoplasticresin and their composite material. As an alternative to this, theforegoing photosensitive resin of a type having photosensitivecharacteristic imparted thereto may be employed. When the photosensitiveresin is employed, exposure and development processes of the interlayerresin insulating layers can be performed to form the openings for thevia holes.

In particular, it is preferable that the resin containing thermosettingresin is employed. In the foregoing case, the shape of the rough surfacecan be maintained against plating solution and when a variety of heatingprocesses are performed.

The refractory resin is exemplified by epoxy resin, phenol resin,phenoxy resin, polyimide resin, polyphenylene resin, polyolefin resinand fluorine resin. The foregoing material may be employed solely or twoor more types of the materials may be mixed.

It is preferable that epoxy resin having two or more epoxy groups in onemolecule thereof is employed. The reason for this lies in that theforegoing rough surface can be formed. Moreover, excellent heatresistance and the like can be obtained. Thus, concentration of stressonto the metal layer can be prevented even under a heat cycle condition.Thus, occurrence of separation of the metal layer can be prevented.

The epoxy resin is exemplified by cresol novolac epoxy resin,bisphenol-A epoxy resin, bisphenol-F epoxy resin, phenol novolac epoxyresin, alkylphenol novolac epoxy resin, biphenol-F epoxy resin,naphthalene epoxy resin, dicyclopentadiene epoxy resin, an epoxymaterial constituted by a condensation material of phenol and anaromatic aldehyde having a phenol hydroxyl group, triglycidylisocyanurate and alicyclic epoxy resin. The foregoing material may beemployed solely or two or more material may be mixed. Thus, excellentheat resistance can be realized.

It is preferable that the soluble particles in the resin film accordingto the present invention are substantially uniformly dispersed in therefractory resin. The reason for this lies in that a rough surfacehaving uniform pits and projections can be formed. When via holes andthrough holes are formed in the resin film, adhesiveness with the metallayer of the conductor circuit can be maintained. As an alternative tothis, a resin film containing soluble particles in only the surface onwhich the rough surface is formed may be employed. Thus, the portions ofthe resin film except for the surface is not exposed to acid or theoxidizer. Therefore, the insulating characteristic between conductorcircuits through the interlayer resin insulating layer can reliably bemaintained.

It is preferable that the amount of the soluble particles which aredispersed in the refractory resin is 3 wt % to 40 wt % with respect tothe resin film. When the amount of mixture of the soluble particles islower than 3 wt %, the rough surface having required pits andprojections cannot be formed. When the amount is higher than 40 wt %,deep portions of the resin film are undesirably dissolved when thesoluble particles are dissolved by using acid or the oxidizer. Thus, theinsulating characteristic between the conductor circuits through theinterlayer resin insulating layer constituted by the resin film cannotbe maintained. Thus, short circuit is sometimes is caused to occur.

It is preferable that the resin film contains a curing agent and othercomponents as well as the refractory resin.

The curing agent is exemplified by an imidazole curing agent, an aminecuring agent, a guanidine curing agent, an epoxy adduct of each of theforegoing curing agents, a microcapsule of each of the foregoing curingagents and an organic phosphine compound, such as triphenylphosphine ortetraphenyl phosphonium tetraphenyl borate.

It is preferable that the content of the curing agent is 0.05 wt % to 10wt % with respect to the resin film. When the content is lower than 0.05wt %, the resin film cannot sufficiently be hardened. Thus, introductionof acid and the oxidizer into the resin film occurs greatly. In theforegoing case, the insulating characteristic of the resin filmsometimes deteriorates. When the content is higher than 10 wt %, anexcessively large quantity of the curing agent component sometimesdenatures the composition of the resin. In the foregoing case, thereliability sometimes deteriorates.

The other components are exemplified by an inorganic compound which doesnot exert an influence on the formation of the rough surface and afiller constituted by resin. The inorganic compound is exemplified bysilica, alumina and dolomite. The resin is exemplified by polyimideresin, polyacrylic resin, polyamideimide resin, polyphenylene resin,melanine resin and olefin resin. When any one of the foregoing fillersis contained, conformity of the thermal expansion coefficients can beestablished. Moreover, heat resistance and chemical resistance can beimproved. As a result, the performance of the printed circuit board canbe improved.

The resin film may contain solvent. The solvent is exemplified byketone, such as acetone, methylethylketone or cyclohexane; aromatichydrocarbon, such as ethyl acetate, butyl acetate, cellosolve acetate,toluene or xylene. The foregoing material may be employed solely or twoor more materials may be mixed.

(4) Next, penetrating holes 35 each having a diameter of 300 μm areformed in the core substrate 30 to which the resin films 50α have beenbonded, for forming through holes (FIG. 1(E)).(5) Via hole openings 52 each having a diameter of 80 μm are formed inthe resin films 50 α by applying carbonic acid, excimer, YAG or UV laser(FIG. 2(A)). Thereafter, the resin films 50 α are thermally hardened tothereby form lower interlayer resin insulating layers 50. The via holesmay be formed by an area process using laser or an area process usinglaser with masks mounted. Alternatively, mixture laser (which means amixture of, for example, carbonic acid laser and excimer laser) may beemployed. Alternatively, both the through holes and the via holes may beformed by using laser.(6) Next, an oxidizer consisting of a chromic acid or a permanganate(e.g., potassium permanganate or sodium permanganate) is used to subjectthe penetrating holes 35 for forming through holes formed in the coresubstrate 30 and the lower interlayer resin insulating layers 50 to ade-smear process and, at the same time, the surfaces of the lowerinterlayer resin insulating layers 50 are roughened (FIG. 2(B)). Whiletemperature for performing these processes is set at 65° C. wherein, theprocesses may be performed at temperature which fall within a range of40 to 70° C.

The rough surfaces of the interlayer resin insulating layers are formedto have a thickness in a range of 0.5 to 5 mm. The thickness in thatrange can ensure adhesiveness and the interlayer resin insulating layerscan be removed in a later step.

The multi-layer printed circuit board in the first embodiment has thecore substrate 30 consisting of one of an FR4 resin, an FR5 resin or aBT resin and has the lower interlayer resin insulating layers 50containing at least one of an epoxy resin, a phenol resin, a polyimideresin, a polyphenylene resin, a polyolefin resin, a fluorocarbon resin.It is, therefore, possible to simultaneously perform the de-smearprocess using an oxidizer consisting of a chromic acid and apermanganate to the through holes 35 and the roughing process to thelower interlayer resin insulating layers 50. Thus, the number of stepsis reduced to thereby manufacture the multi-layer printed circuit boardat low cost. An electroless plated film is formed to have a thickness ina range of 0.1 to 5 μm. If having a thickness in that range, theelectroless plated film can be formed entirely and easily etched away.

(7) A palladium catalyst is applied to the roughed surfaces of theinterlayer resin insulating layers 50 to form electroless copper platedfilms 42 in an electroless plating solution (FIG. 2(C)). While theelectroless copper plated films are formed herein, copper or nickelcoats may be formed by sputtering. Alternatively, the surface layers maybe subjected to a plasma, UV or corona process as a drying process.Through the process, the surfaces of the layers 50 are reformed.(8) After washing the substrate on which the electroless copper platedfilms 42 have been formed, plating resists 43 each having apredetermined pattern are formed (FIG. 2(D)).(9) The substrate is immersed in an electroplating solution to supply anelectric current thereto through the electroless copper plated films 42,thereby forming electroplated copper films 44 (FIG. 2(E)).(10) The plating resists 43 are separated and removed with KOH and theelectroless copper plated films 42 under the plating resists are etchedaway by light etching, thereby forming via holes 46 and through holes 36each consisting of the electroless copper plated film 42 and theelectroplated copper film 44 (FIG. 3(A)).(11) A rough layer (made of an alloy consisting of Cu—Ni—P) 47 is formedin each of the via holes 46 and the through holes 36 by electrolessplating (FIG. 3(B)). Instead of electroless copper plating, the roughlayer can be formed by etching (e.g., etching by spraying or immersingthe holes by or into a solution of a mixture of a cupric complex and anorganic acid salt) or by an oxidization-reduction process.(12) Resin filler 54 is prepared to have a viscosity of 50 Pa·S at 23°C., masks having openings according to the diameters of the throughholes 36 and the via holes 46, respectively, are mounted, the resinfiller 54 is filled by printing and dried in a drying furnace at atemperature of 100° C. for 20 minutes (FIG. 3(C)). In the firstembodiment, the same filler is simultaneously filled in the throughholes 36 and the via holes 46, so that the number of manufacturing stepscan be reduced.

Here, as the resin filler, the following material compositions can beemployed:

[Resin Composition]

100 parts by weight of bisphenol F epoxy monomer (YL983U having amolecular weight of 310 and manufactured by Yuka Shell), 72 parts byweight of SiO₂ spherical particles having a surface coated with a silanecoupling agent and having a mean particle diameter of 1.6 μm (CRS101-1-CE manufactured by Admatec, where the maximum particle size is notlarger than the thickness (15 μm) of an inner-layer copper pattern to bedescribed later), 6.5 parts by weight of an imidazole curing agent(2E4MZ-CN manufactured by Shikoku Chemicals) and 1.5 parts by weight ofa leveling agent (PERENOL S4 manufactured by SANNOPCO) are stirred andmixed to thereby adjust the viscosity of the resultant mixture to 36,000to 49,000 cps at 23±1° C.

(13) One side of the substrate 30 for which the process of (12) has beencompleted, is polished so as to flatten the surface of the resin filler54 protruding from the openings of the via holes 46 and the throughholes 36. Then, buffing is conducted once or a plurality of times toremove flaws caused by polishing. The series of polishing processes arealso conducted to the other side of the substrate (FIG. 3(D)).

It is noted that the protruded resin filler can be removed and flattenedonly by buffing.

The advantage of conducting buffing is that various types of particlesare contained in the interlayer resin insulating layers and are notscraped away during polishing.

Next, the resin filler 54 is hardened by conducting a heat process at100° C. for one hour and at 150° C. for one hour.

Thus, a resin filler layer having the hardened resin filler containingthe epoxy resin, the curing agent and the inorganic particles, is formedin each through hole.

While the epoxy resin is not limited to a particular resin, it ispreferably at least one selected from a group consisting of bisphenolepoxy resins and novolac resins. This is because if a bisphenol A or Fepoxy resin is selected, the viscosity of the resultant mixture can beadjusted without using a dilution solvent. In addition, novolac epoxyresins are excellent in strength, heat resistance and chemicalresistance, are not decomposed even in a strong base solution such aselectroless plating solution and are not thermally decomposed.

As the bisphenol epoxy resin, a bisphenol A epoxy resin or a bisphenol Fepoxy resin is preferable. The bisphenol F epoxy resin is morepreferable because it can be employed with a low viscosity and withoutusing a solvent.

Further, as the novolac epoxy resin, at least one selected from phenolnovolac epoxy resins and cresol novolac epoxy resins is preferable.

Alternatively, a mixture of a bisphenol epoxy resin and a novolac epoxyresin may be employed.

In the latter case, a mixture ratio of, for example, the bisphenol epoxyresin to the cresol novolac epoxy resin is preferably 1/1 to 1/100. Bymixing the bisphenol epoxy resin and the cresol novolac epoxy resin witheach other in that range, it is possible to suppress the viscosity ofthe resultant mixture from rising.

The curing agent contained in the resin filler is not limited to aparticular one and a well-known curing agent is available; however, animidazole curing agent or an amine curing agent is preferable. If such acuring agent is employed, the contraction degree of the filler when thefiller is hardened is small and the adhesiveness between the conductorlayer constituting the through holes and the resin filler layer isparticularly excellent.

Further, the inorganic particles contained in the resin filler mayconsist of, for example, aluminum compounds, calcium compounds,potassium compounds, magnesium compounds, silicon compounds and thelike. They may be used solely or two or more of them may be employed.

The aluminum compounds involve, for example, alumina, aluminum hydroxideand the like. The calcium compounds involve, for example, calciumcarbonate, calcium hydroxide and the like. The magnesium compoundsinvolve, for example, magnesia, dolomite, basic magnesium carbonate,talc and the like. The silicon compounds involve, for example, silica,zeolite and the like.

The resin filler contains inorganic particles of 10 to 50 wt %. Theinorganic particle content in that range allows matching thermalexpansion coefficients between the interlayer resin insulating layers.It is more preferable that the resin filler contains inorganic particlesof 20 to 40 wt %.

The shapes of the inorganic particles involve spherical, circular,ellipsoidal, pulverized, polygonal shapes. Among them, the spherical,circular and ellipsoidal shapes are more preferable. This is becausethese shapes can suppress the occurrence of cracks and the likeresulting from particle shapes. Further, the particles may be coatedwith a silica coupling agent. By doing so, the adhesiveness between theinorganic particles and the epoxy resin improves.

It is also preferable that a rough surface is formed on at least part ofthe surface of the conductor layers constituting the through holes. Ifso, the adhesiveness between the conductor layers and the resin fillerlayers further improves and expansion and contraction in a heat historycan be suppressed to thereby make it more difficult to separate theconductor layers from the resin filler layers. The mean roughness of therough surface is preferably 0.05 to 5 μm. If the mean roughness is lessthan 0.05 μm, the effect of roughing the surfaces of the conductorlayers is hardly obtained. If the mean roughness exceeds 5 μm, signaldelays and signal errors resulting from a skin effect at the time ofsignal transmission may possibly occur.

The resin filler may contain not only the epoxy resin but also otherthermosetting resins, thermoplastic resins, photosensitive resins,complexes thereof or the like.

The thermosetting resins involve, for example, a polyimide resin and aphenol resin. The thermoplastic resins involve, for example, afluorocarbon resin such as polytetrafluoroethylene (PTFE),tetrafluoroethylene/hexafluoropropylene copolymer (fluorinated ethylenepropylene) (FEP) and tetrafluoroethylene/perphloroalkoxy copolymer(PFA), polyethylene terephthalate (PET), polysulfone (PSF),polyphenylene sulfide (PPS), thermoplastic polyphenylene ether (PPE),polyether sulfone (PES), polyetherimide (PEI), polyphenylene sulfone(PPES), polyethylene naphthalate (PEN), poly(ether ether ketone) (PEEK),polyolefin and phenoxy resins. The photosensitive resins involve, forexample, acrylic resins by adding a (meta) acrylic acid havingphotosensitive groups to part of thermosetting resins. There resins maybe used solely or two or more resins may be employed. Instead of theepoxy resin, these resins or complexes thereof (i.e., a complex of athermosetting resin and a thermoplastic resin or a complex of aphotosensitive resin and a thermoplastic resin) may be employed.

Further, resin particles, metallic particles and the like other than theinorganic particles may be mixed with the resin filler. The resinparticles involve those obtained by sphering thermosetting resins,thermoplastic resins and the like. The metallic particles involveconductive particles such as gold, silver and copper particles and thelike. They may be used solely or two types or more particles may beemployed. Alternatively, they may be employed instead of the inorganicparticles.

The resin filler may contain a solvent such as NMP(N-methylpyrrolidone), DMDG (diethylene glycol dimethyl ether),glycerol, cyclohexanol, cyclohexanone, methyl cellosolve, methylcellosolve acetate, methanol, ethanol, butanol or propanol,(solvent-impregnated type); however, it is more preferable that theresin filler contains no solvent (non-solvent-containing type). This isbecause air bubble is less left in the through holes and the like afterhardening the resin filler if the resin filler contains no solvent. Ifair bubble is left, reliability and connection characteristicsdeteriorate.

(14) A palladium catalyst is applied to the surfaces of the interlayerresin insulating layers 50 to thereby form electroless copper platedfilms 56 in an electroless plating solution (FIG. 4(A)). While theelectroless copper plated films are formed herein, copper or nickelcoats can be formed by sputtering. In some cases, electroplating can bedirectly performed to the interlayer resin insulating layers 50.(15) After forming plating resists (not shown) each having apredetermined pattern, electroplated copper films 57 are formed. Then,the plating resists are separated and removed and the electroless copperplated films 56 under the plating resist are separated by light etching,thereby forming plated covers 58 each consisting of the electrolesscopper plated film 56 and the electroplated copper film 57 in theopening portions of the via holes 46 and the through holes 36,respectively (FIG. 4(B)).(16) Rough layers (Cu—Ni—P) are formed on the plated covers 58 providedon the openings of the via holes 46 and the through holes 36 byelectroless plating, respectively (FIG. 4(C)). The rough layers can beformed by etching or an oxidization-reduction process instead of theelectroless copper plating.(17) By repeating the steps (3) to (11) described above, upperinterlayer resin insulating layers 60 are formed and via holes 66 eachconsisting of the electroless copper plated film 62 and theelectroplated copper film 64 on the upper interlayer resin insulatinglayers 60 (FIG. 4(D)).(18) Next, solder resists and solder bumps are formed. The materialcomposition of the solder resist is as follows.

46.67 g of oligomer (having a molecular weight of 4000) which isobtained by forming 50% of epoxy groups of 60 wt % cresol novolac epoxyresin (manufactured by Nippon Kayaku) dissolved in DMDG into an acrylicstructure and which imparts photosensitive characteristic, 15.0 g of 80wt % bisphenol A epoxy resin (Epicoat 1001 manufactured by Yuka Shell)dissolved in methyl ketone, 1.6 g of an imidazole curing agent (2E4MZ-CNmanufactured by Shikoku Chemicals), 3 g of polyhydric acrylic monomerwhich is photosensitive monomer (R604 manufactured by Nippon Kayaku),1.5 g of polyhydric acrylic monomer (DPE6A manufactured by KyoeiChemical) and 0.71 g of a dispersing deforming agent (S-65 manufacturedby SANNOPCO) are mixed with one another. Then, 2 g of benzophenone(manufactured by Kanto Chemical) serving as a photoinitiator and 0.2 gof Michler's ketone (manufactured by Kanto Chemical) serving as aphotosensitizer are added to the resultant mixture, thereby obtaining asolder resist composition having a viscosity adjusted to 2.0 Pa·s at 25°C.

For the solder resist layers, various types of resins may be used. Forexample, a resin obtained by hardening a bisphenol A epoxy resin, abisphenol A epoxy acrylate resin, a novolac epoxy resin or a novolacepoxy acrylate resin by an amine curing agent, an imidazole curing agentor the like can be used.

In case of forming a solder bump by providing an opening in the solderresist layer, in particular, it is preferable to use a resin containing“a novolac epoxy resin or a novolac epoxy acrylate resin” and containing“an imidazole curing agent” as a curing agent.

The above solder resist composition 70α is applied to each side of themulti-layer printed circuit board obtained in the step (17) to have athickness of 40 μm (FIG. 5(A)).

(19) Then, a drying process is performed at 70° C. for 20 minutes and at80° C. for 30 minutes. Thereafter, a photomask film which has athickness of 5 mm and on which a circular pattern (mask pattern) drawnis made hermetic contact with the both sides of the resultantmulti-layer printed circuit board, mounted thereon, exposed withultraviolet rays with 1000 mj/cm² and subjected to a DMTG developmentprocess. Further, a heat process is performed on conditions of 80° C.for one hour, 100° C. for one hour, 120° C. for one hour and 150° C. forthree hours, to thereby form solder resist layers 70 (a thickness of 20μm) each having opening portions 71 (an opening diameter of 200 μm)(FIG. 5(B)).(20) Thereafter, the multi-layer printed circuit board is immersed in anelectroless nickel plating solution composed of 2.3×10⁻¹ mol/l sodiumhypophosphite and 1.6×10⁻¹ mol/l sodium citrate and having pH=4.5 for 20minutes. Thus, a nickel plated layer 72 having a thickness of 5 μm isformed in each opening portion 71. Then, the multi-layer printed circuitboard is immersed in an electroless gold plating solution composed of7.6×10⁻³ mol/l gold potassium cyanide, 1.9×10¹ mol/l ammonia chloride,1.2×10⁻¹ mol/l sodium citrate and 1.7×10⁻¹ mol/l sodium hypophosphite onconditions of 80° C. for 7.5 minutes. Thus, gold plated layers 74 eachhaving a thickness of 0.03 μm are formed on the nickel plated layers 72,respectively (FIG. 5(C)).

In the above-stated case, the intermediate layer is formed out of nickeland the noble metal layer out of gold. Alternatively, the intermediatelayer may be formed out of palladium, tin or titanium instead of nickeland the noble metal layer may be formed out of silver, platinum or thelike other than gold. Two or more noble metal layers may be formed. Assurface processes, a drying process, a plasma process, a UV process anda corona process may be performed. By doing so, it is possible toenhance the filling efficiency of the under-filler for the IC chip.

(23) Then, a solder paste is printed on each opening 71 of the solderresist layer 70 and a reflow process is conducted to thereby form asolder bump (solder) 76 in each of the upper surface-side via holes 66.Also, a conductive connection pin 78 is attached to each of the lowersurface-side via holes 66 through the solder 77 (see FIG. 6). It is alsopossible to form a BGA instead of the conductive connection pin.

As the solder, Sn/Pb, Sn/Sb, Sn/Ag, Sn/Sb/Pb, Sn/Ag/Cu and the like maybe used.

The melting point of the solder is preferably 180 to 280° C. The solderhaving the melting point in that range can ensure that the conductiveconnection pin has a strength of 2.0 Kg/pin or higher. If the meltingpoint is lower than that range, the strength of the pin decreases. Ifexceeding the range, the solder resist layer may possibly be dissolved.It is particularly preferable that the melting point of the solder is200 to 260° C.

It is more preferable that the melting point of the solder at theconductive connection pin side is higher than that of the solder at thesolder bump side. By doing so, conductive connection pins are notinclined or detached during reflow if an IC chip is mounted as a flipchip. A combination of solders is, for example, Sn/Pb at the solder bumpside and Sn/Sb at the conductive connection pin side.

Comparison Example 1

As a comparison example 1, a multi-layer printed circuit board wasobtained which board is the same in constitution as the multi-layerprinted circuit board in the first embodiment shown in FIG. 1 and whichhas lower via holes filled with copper plated layer. The evaluationresults of the multi-layer printed circuit board in the first embodimentand that in the comparison example 1 are shown in FIG. 7.

Electrical connection characteristic was evaluated by inspectingcontinuity using a checker. If short circuit and disconnection occurred,the multi-layer printed circuit board was judged NG and otherwise,judged OK. The separation and expansion thereof were inspected bycutting the multi-layer printed circuit boards in cross section after aheat cycle test (in which 1000 cycles were repeated with one cycle setas −65° C./3 minutes+130° C./3 minutes) and then visually inspecting theseparation and expansion of the interlayer resin insulating layers andthe via holes using a microscope (×100 to 400).

In the comparison example 1, dents which were not completely filled witha plated material were formed on the surfaces of the lower via holes andthe connection characteristic between the upper and lower via holesdeteriorated. Due to this, there were some via holes which were notelectrically connected to each other.

Further, after the heat cycle test, it was observed that because of theseparation between the via holes, the separation and expansion occurredto the interlayer resin insulating layers. In the multi-layer printedcircuit board in the first embodiment, the connection characteristicsdid not deteriorate and the separation and expansion were not observed.

Comparison Example 2

As a comparison example 2, a multi-layer printed circuit board wasobtained which board is the same in constitution as the multi-layerprinted circuit board in the first embodiment shown in FIG. 6 and whichhas the resin filler used in the first embodiment and filled in throughholes and has a metal paste mainly consisting of a silver paste andfilled in via holes. In the multi-layer printed circuit board in thecomparison example 2, the coefficient of the thermal expansion of thevia holes 66 filled with the metal paste greatly differed from that ofthe through holes 26 filled with the resin filler. Due to this, a forcetransferred to the lower interlayer resin insulating layers 50 from thelateral direction varies and the interlayer resin insulating layers 50expanded or separated from a core substrate 30. In the embodiment statedabove, by contrast, the separation of the lower interlayer resininsulating layers 50 did not occur.

When a heat cycle test was conducted (in which 1000 cycles were repeatedwith one cycle set as −65° C./3 minutes+130° C./3 minutes), theconnection characteristics and adhesiveness did not deteriorate in theembodiment. In the comparison example 2, because of the difference infiller material, it was observed that the adhesiveness of some partsdeteriorated and the separation of the interlayer resin insulatinglayers occurred.

Comparison Example 3

A comparison example 3 is almost the same as the first embodiment exceptthat the quantity of mixed silica was 271 parts by weight and that themixture ratio of inorganic particles to resin filler was 71.5 wt %.

Comparison Example 4

A comparison example 4 is almost the same as the first embodiment exceptthat the quantity of mixed silica was 5.7 parts by weight and that themixture ratio of inorganic particles to resin filler was 5.0 wt %.

In the comparison example 3, it was observed that cracks occurred to theresin filler under heat cycle conditions. In the comparison example 4,the surface portion of the resin filler was not polished flat andinsufficiently polished portions and recessed portions resulting fromthe separation of inorganic particles were observed. Further, it wasobserved that the thicknesses of the plated films on the resin fillerwere uneven or the plated films were not deposited.

Second Embodiment

The constitution of a printed circuit board according to the secondembodiment of the present invention will be described hereinafter withreference to FIG. 13 which is a cross-sectional view of a printedcircuit board 110.

The printed circuit board 110 consists of a core substrate 130 andbuildup wiring layers 180A and 180B. Each of the build up wiring layers180A and 180B consists of interlayer resin insulating layers 150 and160. Via holes 146 and conductor circuits 145 are formed on theinterlayer resin insulating layers 150. Via holes 166 and conductorcircuits 165 are formed on the interlayer resin insulating layers 160.Solder resist layers 170 are provided on the respective interlayer resininsulating layers 160.

Next, description will be given to a method of manufacturing the printedcircuit board according to the second embodiment of the presentinvention. Here, A. interlayer resin insulating films used formanufacturing the printed circuit board in the second embodiment will bedescribed, while B. resin filler will not be described since the resinfiller is the same in material composition as the resin filler used inthe first embodiment.

A. Manufacture of a Resin Film for Forming the Interlayer ResinInsulating Layers:

30 parts by weight of a bisphenol A epoxy resin (Epicoat 1001 having anepoxy equivalent of 469 and manufactured by Yuka Shell), 40 parts byweight of a cresol novolac epoxy resin (Epichron N-673 having an epoxyequivalent of 215 and manufactured by Dainippon Ink & Chemicals) and 30parts by weight of a phenol novolac resin containing triazine structure(Phenolight KA-7052 having a phenol hydroxyl group equivalent of 120 andmanufactured by Dainippon Ink & Chemicals) were heated and dissolved in20 parts by weight of ethyl diglycol acetate and 20 parts by weight ofsolvent naphtha while being stirred. Then, 15 parts by weight ofpolybutadiene rubber having epoxy terminal (Denalex R-45EPT manufacturedby Nagase Chemicals), 1.5 parts by weight of pulverized2-phenyl-4,5bis(hydroxymethyl) imidazole, 2 parts by weight ofparticle-size reduced silica and 0.5 parts by weight of a silicondefoaming agent were added thereto, thus preparing an epoxy resincomposition. The obtained epoxy resin composition was applied onto a PETfilm having a thickness of 38 μm by using a roll coater so that thethickness of the film was 50 μm after the film was dried, and dried at80 to 120° C. for 10 minutes, thereby manufacturing the resin film forforming an interlayer resin insulating layer.

The description of the method of manufacturing the printed circuit boardstated above with reference to FIG. 13 will be continued with referenceto FIGS. 8 to 13.

(1) A copper-clad laminated plate 130A having copper foils 132 eachhaving a thickness of 18 μm and laminated on the both sides of asubstrate 130 having a thickness of 0.8 mm and made of a glass epoxyresin or a BT (Bismaleimide-Triazine) resin is employed as a startingmaterial (FIG. 8(A)). First, this copper-clad laminated plate 130A isdrilled, subjected to an electroless plating process and etched in apattern fashion, thereby forming lower conductor circuits 134 andthrough holes 136 on the both sides of the substrate 130 (FIG. 8(B)).(2) After washing and drying the substrate 130 on which the throughholes 136 and the lower conductor circuits 134 have been formed, ablackening process using a solution containing NaOH (10 g/l), NaClO₂ (40g/l) and Na₃PO₄ (6 g/l) as a blackening bath (oxidization bath) and areduction process using a solution containing NaOH (10 g/l) and NaBH₄ (6g/l) as a reduction bath are conducted to thereby form rough layers 134αand 136α on the entire surfaces of the lower conductor circuits 134including the through holes 136 (FIG. 8(C)). The roughing process may besurface roughing or the like by conducting soft etching, by forming aneedle-type alloy plated material consisting ofcopper-nickel-phosphorous (Interplate manufactured by EBARA UDYLITE Co.,Ltd.) or by using an etching solution such as “MEC etch BOND”manufactured by Mec Co., Ltd.(3) Next, the surfaces of the lands 136 a of the through holes 136having the rough layers 136α formed thereon, respectively, are polishedby buffing and the rough layers 136α of the lands 136 a are separated toflatten the surfaces of the lands 136 a (FIG. 8(D)).(4) The resin filler described in B above is prepared, a mask 139 havingopening portions 139 a corresponding to the respective through holes 36is mounted on the substrate 130 within 24 hours of the preparation ofthe resin filler, and the resin filler 154 is pushed into the throughholes 136 using a squeegee and dried on conditions of 100° C. for 20minutes (FIG. 9(A)). In the step of (3) above, after forming the roughlayers 136α on the through holes 136, the surfaces of the lands 136 a ofthe through holes 136 are polished and flattened. Due to this, whenfilling the resin filler in the through holes 136, it is possible toprevent the resin filler 154 from flowing out along the rough layers(anchors) formed on the lands 136 a of the through holes 136. It is,therefore, possible to form the filler 154 in the through holes flat andto enhance the reliability of wirings above the through holes to beformed in a step described later.

Furthermore, the layers of resin filler 154 are formed on portions onwhich the lower conductor circuits 134 are not formed using a squeegeeand dried on conditions of 100° C. for 20 minutes (FIG. 9(B)). As theresin filler 154, it is preferable to employ one selected from a mixtureof an epoxy resin and organic filler, a mixture of an epoxy resin andinorganic filler and a mixture of an epoxy resin and inorganic fiber.Alternatively, the resin filler in the first embodiment may be employed.

(5) One side of the substrate 130 for which the process described in (4)above has been completed, is polished by belt sander polishing using#600 belt abrasive paper (manufactured by Sankyo) in such a manner thatthe resin filler 154 is not left on the surfaces of the lower conductorcircuits 134 and those of the lands 136 a of the through holes 136.Then, buffing is performed to remove flaws caused by the belt sanderpolishing. These series of polishing are also conducted to the otherside of the substrate 130 (FIG. 9(C)). Next, the resin filler 154 ishardened by performing a heating process at 100° C. for one hour and150° C. for one hour.

Thus, the surface portion of the resin filler 154 filled between thelower conductor circuits 134 and in the through holes 136 and the roughsurfaces 134α on the upper surfaces of the lower conductor circuits 134are removed to thereby flatten the both sides of the substrate. By doingso, it is possible to obtain a wiring substrate in which the resinfiller 154 and, the lower conductor circuits 134 and the through holes136 are fixedly bonded through the rough layers 134α and 136α.

(6) After washing the substrate 130 and degreasing the substrate 130with an acid, the substrate 130 is subjected to soft etching and anetching solution is sprayed on the both sides of the substrate 130 toetch the surfaces of the lower conductor circuits 134 and the surfacesof the lands 136 a of the through holes 136, thereby forming roughsurfaces 134β on the entire surfaces of the lands 136 a of the throughholes 136 and the lower conductor circuits 134 (FIG. 9(D)). As theetching solution, an etching solution containing 10 parts by weight ofimidazole copper (II) complex, 7 parts by weight of a glycolic acid and5 parts by weight of potassium chloride (MEC etch BOND manufactured byMec Co., Ltd.) Each of the rough layers thus formed preferably has athickness in a range of 0.1 to 5 μm. In that range, the separationbetween the conductor circuits and the interlayer resin insulatinglayers less occurs.(7) Resin films for forming interlayer resin insulating layers slightlylarger than the substrate 130 manufactured in A are mounted on the bothsides of the substrate 130, temporarily pressed on conditions of apressure of 4 kgf/cm², a temperature of 80° C. and a press duration of10 seconds and cut. Then, the resin films are bonded using a vacuumlaminator device by the following method, thereby forming interlayerresin insulating layers 150 on the both sides of the substrate 130 (FIG.10(A)). Namely, the resin films for forming the interlayer resininsulating layers are actually pressed on the both sides of thesubstrate on conditions of the degree of vacuum of 0.5 Torr, a pressureof 4 kgf/cm², a temperature of 80° C. and a press duration of 60 secondsand then thermally hardened at 170° C. for 30 minutes.(8) Next, via hole openings 152 each having a diameter of 80 μm areformed on the interlayer resin insulating layers 150 through masks 151each having a thickness of 1.2 mm and having penetrating holes 151 aformed therein, by using CO₂ gas laser at a wavelength of 10.4 μm onconditions of a beam diameter of 4.0 mm, a top-hat mode, a pulse widthof 8.0 microseconds, the diameter of each penetrating hole 151 a of themasks 151 of 1.0 mm and one shot (FIG. 10(B)).(9) The substrate 130 having the via hole openings 152 formed therein isimmersed in a solution containing 60 g/l of a permanganate acid at atemperature of 80° C. and epoxy resin particles existing on the surfacesof the interlayer resin insulating layers 150 are dissolved and removed,thereby forming rough surfaces 150α on the surfaces of the interlayerresin insulating layers 150 including the inner walls of the via holeopenings 152 (FIG. 10(C)). The rough surfaces of the interlayer resininsulating layers are formed to have a thickness in a range of 0.5 to 5μm. In that range, adhesiveness can be ensured and the conductor layerscan be removed in a later step.(10) Next, the substrate 130, for which the above stated processes havebeen completed, is immersed in a neutral solution (manufactured bySiplay) and washed. A palladium catalyst is applied to the surfaces ofthe substrate 130 which surfaces have been roughed (with a rough depthof 3 μm), thereby attaching catalyst cores on the surfaces of theinterlayer resin insulating layers 150 and the inner wall surfaces ofthe via hole openings 152.(11) Then, the substrate 130 is immersed in an electroless copperplating solution having the following composition to form electrolesscopper plated films 156 each having a thickness of 0.5 to 5.0 μm on theentire rough surfaces 150α (FIG. 10(D)).

[Electroless Plating Solution] NiSO₄ 0.003 mol/l tartaric acid 0.200mol/l copper sulfate 0.030 mol/l HCHO 0.050 mol/l NaOH 0.100 mol/lα,α-bipyridyl 40 mg/l polyethylene glycol (PEG) 0.10 g/l

[Electroless Plating Conditions]

40 minutes at a solution temperature of 35° C.

(12) Commercially available photosensitive dry films are bonded onto theelectroless copper plated films 156. Masks are mounted on the films,respectively and the films are exposed with 100 mj/cm² and developedwith a 0.8% sodium carbonate solution, thereby providing plating resists155 each having a thickness of 30 μm. Then, the substrate 130 is washedwith water of a temperature of 50° C. and degreased, washed with waterof a temperature of 25° C. and with a sulfuric acid, and subjected tocopper electroplating on the following conditions, thereby formingelectroplated copper films 157 each having a thickness of 20 μm (FIG.11(A)).

[Electroplating Solution] Sulfuric acid 2.24 mol/l Copper sulfate 0.26mol/l Additive 19.5 mol/l(Kaparacid HL manufactured by Atotech Japan)

[Electroplating Conditions] Current density 1 A/dm² Duration 65 minutestemperature 22 ± 2° C.(13) After separating and removing the plating resists 155 with 5% NaOH,the electroless plated films 156 under the plating resists 155 areetched with a solution mixture of a sulfuric acid and hydrogen peroxideto remove and dissolve the films 156, thereby forming conductor circuits145 (including via holes 146) each consisting of the electroless copperplated film 156 and the electroplated copper film 157 and having athickness of 18 μm (FIG. 11(B)).(14) The same process as that in (6) is performed, i.e., rough surfaces145α are formed on the respective conductor circuits 145 by employing anetching solution containing a cupric complex and an organic acid (FIG.11(C)).(15) The steps of (7) to (14) are repeated, thereby forming interlayerresin insulating layers 160 and conductor circuits 165 (including viaholes 166) further above (FIG. 11(D)).(16) Next, a solder resist composition prepared in the same manner asthat in the first embodiment is obtained.(17) The solder resist composition is applied to each side of thesubstrate 130 to have a thickness of 20 μm and dried. Then, a photomaskis closely attached to each solder resist layer 170, exposed toultraviolet rays, developed with a DMTG solution to form openings 171Uand 171D each having a diameter of 200 μm. Thereafter, a heating processis performed to harden the solder resist layers 170 to thereby providethe solder resist layers 170 each having openings 171U and 171D and eachhaving a thickness of 20 μm (FIG. 12(A)). The solder resist compositionmay be a commercially available solder resist composition.(18) The substrate 130 having the solder resist layers 170 formedthereon is immersed in the same electroless nickel plating solution asthat employed in the first embodiment and then immersed in anelectroless gold plating solution, thereby forming a nickel plated layer172 and a gold plated layer 174 in each of the openings 171U and 171D(FIG. 12(B)).(19) Thereafter, a solder paste containing tin-lead is printed on eachopening 171U of the solder resist layers 170 of the substrate 130.Further, a solder paste as a conductive adhesive agent 197 is printed oneach opening 171 at the other side of the substrate. Next, conductiveconnection pins 178 are attached to and supported by an appropriate pinholding device and the fixed portions 198 of the respective conductiveconnection pins 178 are brought into contact with the conductiveadhesive agent 197 within the openings 171D. A reflow process is thenperformed to fix each conductive connection pin 178 to the conductiveadhesive agent 197. Alternatively, to attach the conductive connectionpins 178, the conductive adhesive agent 197 may be formed into a ballshape or the like and put in the openings 171D, or the conductiveadhesive agent 197 may be joined to the fixed portions 198 to attach theconductive connection pins 178, followed by a reflow process. By doingso, it is possible to obtain a printed circuit board 110 having thesolder bumps 176 and the conductive connection pins 178 (FIG. 13).

First Modification of Second Embodiment

A printed circuit board 120 according to the first modification of thesecond embodiment of the present invention will be described hereinafterwith reference to FIG. 19. In the second embodiment stated above, a PGAmethod for establishing connection through the conductive connectionpins 178 as shown in FIG. 13 has been described. The first modificationof the second embodiment is almost the same in constitution as thesecond embodiment except that bumps 176 at a daughter board side areconnected to the daughter board by a BGA method.

Now, a method of manufacturing a printed circuit board according to thefirst modification of the second embodiment will be described withreference to FIGS. 14 to 19.

(1) A copper-clad laminated plate 130A having copper foils 132 eachhaving a thickness of 18 μm and laminated on the both sides of asubstrate 130 having a thickness of 1 mm and made of a glass epoxy resinor a BT (Bismaleimide-Triazine) resin is employed as a starting material(FIG. 14(A)). First, this copper-clad laminated plate 130A is drilledand then a plating resist is formed. Thereafter, the substrate 130 issubjected to an electroless copper plating process to form through holes136 and the copper foils 132 are etched in a pattern fashion accordingto an ordinary method, thereby forming lower conductor circuits 134 onboth sides of the substrate 130 (FIG. 14(B)).(2) After washing and drying the substrate 130 on which the lowerconductor circuits 134 have been formed, an etching solution is sprayedon the both sides of the substrate 130 and the surfaces of the lowerconductor circuits 134, the inner walls of the through holes 136 and thesurf aces of lands 136 a are etched, thereby forming rough layers 134αand 136α on the entire surfaces of the lower conductor circuits 134including the through holes 136 (FIG. 14(C)). As the etching solution, asolution mixture of 10 parts by weight of imidazole copper (II) complex,7 parts by weight of a glycolic acid, 5 parts by weight of potassiumchloride and 78 parts by weight of ion-exchange water is employed. Theroughing process may be performed by conducting soft etching, byconducting a blackening (oxidization)-reduction process or by forming aneedle alloy plated material (Interplate manufactured by EBARA UDYLITECo., Ltd.) consisting of copper-nickel-phosphorous or the like.(3) Next, the surfaces of the lands 136 a of the through holes 136having the rough layers 136α formed thereon, respectively, are polishedby buffing to flatten the surfaces of the lands 136 a (FIG. 14(D)).(4) Next, a mask 139 having opening portions 139 a corresponding to therespective through holes 136 is mounted on the substrate 130 and resinfiller 154 mainly consisting of an epoxy resin is applied using aprinter (FIG. 15(A)). In the step of (3), after forming the rough layers136α on the through holes 136, the surfaces of the lands 136 a of thethrough holes 136 are polished and flattened. Due to this, when fillingthe resin filler in the through holes 136, it is possible to prevent theresin filler 154 from flowing out along the rough layers (anchors)formed on the lands 136 a of the thorough holes 136. It is, therefore,possible to form the filler 154 in the through holes flat and to enhancethe reliability of wirings above the through holes to be formed in astep described later.

Thereafter, using the printer, the resin filler 154 mainly consisting ofan epoxy resin is applied onto the both sides of the substrate 130 anddried. Namely, through this step, the resin filler 154 is filled betweenthe lower conductor circuits 134 (FIG. 15(B)). As the resin filler 154,it is preferable to employ one selected from a mixture of an epoxy resinand organic filler, a mixture of an epoxy resin and inorganic filler anda mixture of an epoxy resin and inorganic fiber. Alternatively, theresin filler in the first embodiment may be employed.

(5) One side of the substrate 130 for which the process described in (4)above has been completed, is polished by belt sander polishing usingbelt abrasive paper (manufactured by Sankyo) in such a manner that theresin filler 154 is not left on the surfaces of the lower conductorcircuits 134 and those of the lands 136 a of the through holes 136.Then, buffing is performed to remove flaws caused by the belt sanderpolishing. These series of polishing are also conducted to the otherside of the substrate 130. The resin filler 154 thus filled is thermallyhardened (FIG. 15(C)).(6) Next, the same etching solution as that employed in (2) above issprayed on the both sides of the substrate 130 for which the processdescribed in (5) above has been completed and the surfaces of the lowerconductor circuits 134 and those of the lands 136 a of the through holes136 which have been flattened once are etched, thereby forming roughsurfaces 134α on the entire surfaces of the lower conductor circuits 134(FIG. 15(D)).(7) Then, thermosetting cycloolefin resin sheets each having a thicknessof 50 μm are laminated by vacuum pressing while raising a temperature to50 to 150° C. and at a pressure of 5 kg/cm² to thereby provideinterlayer resin insulating layers 150 each consisting of a cycloolefinresin (FIG. 16(A)). The degree of vacuum during vacuum pressing is 10mmHg. Alternatively, the resin films employed in the second embodimentmay be employed instead of the above resin sheets.(8) Next, via hole openings 152 each having a diameter of 80 μm areformed on the interlayer resin insulating layers 150 through masks 151each having a thickness of 1.2 mm and having penetrating holes 151 aformed therein, by using CO₂ gas laser at a wavelength of 10.4 μm onconditions of a beam diameter of 5 mm, a top-hat mode, a pulse width of50 microseconds, the diameter of each hole of the masks of 0.5 mm andthree shots (FIG. 16(B)). Then, a de-smear process is performed usingoxygen plasma.(9) Then, using SV-4540 manufactured by ULVAC JAPAN, Ltd., a plasmaprocess is performed to rough the surfaces of the interlayer resininsulating layers 150, thereby forming rough surfaces 150α (FIG. 16(C)).The plasma process is performed for two minutes while using, as inertgas, argon gas on conditions of power of 200 W, a gas pressure of 0.6 Paand a temperature of 70° C. Alternatively, the rough surfaces may beformed by using an acid or an oxidizer.(10) Next, using the same device, the argon gas contained inside isexchanged and sputtering is conducted with Ni and Cu as targets, onconditions of an atmospheric pressure of 0.6 Pa, a temperature of 80°C., power of 200 W and a duration of 5 minutes, thereby forming Ni/Cumetal layers 148 on the surfaces of the respective interlayer resininsulating layers 150. At this time, the thickness of each Ni/Cu metallayer 148 is 0.2 μm (FIG. 16(D)). Electroless copper plated films may befurther formed on the layers 148, respectively, instead of conductingsputtering.(11) Next, commercially available photosensitive dry films are bondedonto the both sides of the substrate 130 for which the above process hasbeen completed. Photomask films are mounted, exposed with 100 mJ/cm² anddeveloped with a 0.8% sodium carbonate solution, thereby forming platingresists 155 each having a thickness of 15 μm. Then, the substrate 130 issubjected to electroplating on the following conditions, thereby formingelectroplated films 157 each having a thickness of 15 μm (FIG. 17(A)).It is noted that an additive in the electroplating solution is KaparacidHL manufactured by Atotech Japan.

[Electroplating Solution] Sulfuric acid 2.24 mol/l Copper sulfate 0.26mol/l Additive 19.5 mol/l

[Electroplating Conditions] Current density 1 A/dm² Duration 65 minutestemperature 22 ± 2° C.(12) After separating and removing the plating resists 155 with 5% NaOH,the Ni/Cu metal layers 148 existing below the plating resists 155 aredissolved and removed by performing etching with a solution mixture of anitric acid, a sulfuric acid and hydrogen peroxide, thereby formingconductor circuits 145 (including via holes 146) each consisting of theelectroplated copper film 157 and the like and having a thickness of 16μm (FIG. 17(B)).(13) Next, the same etching process as that in the step of (6) isperformed to form rough surfaces 145α on the conductor circuits 145,respectively (FIG. 17(C)).(14) By repeating the steps of (7) to (13) above, interlayer resininsulating layers 160 and conductor circuits 165 (including via holes166) are formed further above (FIG. 17(D)).(15) Next, a solder resist composition (organic resin insulatingmaterial) prepared in the same manner as that in the first embodiment isobtained.(16) The solder resist composition is applied to each side of thesubstrate 130 to have a thickness of 20 μm and dried. Then, a photomaskis closely attached to each solder resist layer 170, exposed toultraviolet rays, developed with a DMTG solution to thereby formopenings 171 each having a diameter of 200 μm. Thereafter, a heatingprocess is performed to harden the solder resist layers 170 to therebyprovide the solder resist layers 170 each having openings 171 and havinga thickness of 20 μm (FIG. 18(A)).(17) The substrate 130 having the solder resist layers 170 formedthereon is immersed in an electroless nickel plating solution to formnickel plated layers 172 each having a thickness of 5 μm in therespective openings 171. Further, the substrate 130 is immersed in anelectroless plating solution to thereby form gold plated layers 174 eachhaving a thickness of 0.03 μm on the respective nickel plated layers 172(FIG. 18(B)).(18) Then, a solder paste is printed on each opening 171 of the solderresist layers 170 and a reflow process is performed at 200° C. to formsolder bumps 176, thus manufacturing a printed circuit board 120 havingthe solder bumps 176 (FIG. 19).

Second Modification of Second Embodiment

A printed circuit board according to the second modification is almostthe same as the printed circuit board in the first embodiment describedabove with reference to FIGS. 1 to 6. However, in the secondmodification, as shown in FIG. 20(A), after rough layers (made of analloy consisting of Cu—Ni—P) 47 are formed on via holes 46 and throughholes 36, respectively, by electroless plating, the lands 136 a of thethrough holes 36 on which the rough layers 47 have been formed,respectively, are polished by buffing and flattened (FIG. 20(B)).Thereafter, resin filler 54 is filled in the through holes 36 and thevia holes 46 through masks and dried (FIG. 20(C)). By doing so, it ispossible to prevent the resin filler 54 from flowing out along the roughlayers 47.

Comparison Example 5

A printed circuit board in a comparison example 5 is basically the sameas the printed circuit board in the second embodiment except that theland surfaces of through holes having rough layers formed thereon,respectively, are not polished nor flattened but resin filler is filledin the through holes. The remaining conditions are the same as those inthe second embodiment.

Comparison Example 6

A printed circuit board in a comparison example 6 is basically the sameas the printed circuit board in the first modification of the secondembodiment except that the land surfaces of through holes having roughlayers formed thereon, respectively, are not polished nor flattened butresin filler is filled in the through holes. The remaining conditionsare the same as those in the first modification of the secondembodiment.

Comparison Example 7

A printed circuit board in a comparison example 7 is basically the sameas the printed circuit board in the second modification of the secondembodiment except that the land surfaces of through holes having roughlayers formed thereon, respectively, are not polished nor flattened butresin filler is filled in the through holes. The remaining conditionsare the same as those in the second modification of the secondembodiment.

The printed circuit boards in the second embodiment, the firstmodification and the second modification of the second embodiment werecompared with the printed circuit boards in the comparison examples inrespect of three points, i.e., the roughing method, the surfacepolishing of the lands of the through holes and the flow of the resinfiller out of the through holes. The comparison result is shown in FIG.21. As is obvious from the result shown in FIG. 21, in the printedcircuit boards in the comparison examples 5, 6 and 7, the resin fillerflowed out along the rough layers formed on the lands of the throughholes when filling the resin filler in the through holes because thesurfaces of the lands of the through holes having the rough layersformed thereon, respectively, were not polished.

1. A multi-layer printed circuit board comprising: a core substratehaving a plurality of penetrating holes and having a first surface and asecond surface; a plurality of buildup layers over the first and secondsurfaces of the core substrate, respectively, each of the buildup layerscomprising a plurality of interlayer resin insulating layers and aplurality of conductor layers alternately provided, the plurality ofinterlayer resin insulating layers including a lower interlayer resininsulating layer formed adjacent to the core substrate; a plurality ofthrough holes formed in the plurality of penetrating holes of the coresubstrate, respectively, and through the lower interlayer resininsulating layers and filled with a resin filler including inorganicparticles; and a plurality of via holes filled with a resin fillerincluding inorganic particles and formed in the lower interlayer resininsulating layers.
 2. A multi-layer printed circuit board according toclaim 1, wherein the resin filler in the through holes and the resinfiller in the via holes are a same resin filler.
 3. A multi-layerprinted circuit board according to claim 1, wherein the inorganicparticles in at least one of the resin filler in the through holes andthe resin filler in the via holes comprise at least one compoundselected from the group consisting of aluminum compounds, calciumcompounds, potassium compounds, magnesium compounds and siliconcompounds.
 4. A multi-layer printed circuit board according to claim 1,wherein the inorganic particles in at least one of the resin filler inthe through holes and the resin filler in the via holes comprise atleast one compound selected from the group consisting of alumina,aluminum hydroxide, calcium carbonate, calcium hydroxide, magnesia,dolomite, basic magnesium carbonate, talc, silica and zeolite.
 5. Amulti-layer printed circuit board according to claim 1, wherein at leastone of the resin filler in the through holes and the resin filler in thevia holes contains the inorganic particles in 10 to 50 wt %.
 6. Amulti-layer printed circuit board according to claim 1, wherein at leastone of the resin filler in the through holes and the resin filler in thevia holes contains the inorganic particles in 20 to 40 wt %.
 7. Amulti-layer printed circuit board according to claim 1, wherein theinorganic particles in at least one of the resin filler in the throughholes and the resin filler in the via holes have at least one of aspherical shape, a circular shape, an ellipsoidal shape, a pulverizedshape and a polygonal shape.
 8. A multi-layer printed circuit boardaccording to claim 1, wherein the inorganic particles in at least one ofthe resin filler in the through holes and the resin filler in the viaholes have at least one of a spherical shape, a circular shape and anellipsoidal shape.